Two-cycle lubricating oil compositions



United States Patent 3,544,466 TWO-CYCLE LUBRICATING OIL COMPOSITIONSDonald E. McDowell, Jackson, Jack Ryer, East Brunswick, and Harold E.Deen, Cranford, N.J., assignors to Esso Research and EngineeringCompany, a corporation of Delaware No Drawing. Filed May 16, 1968, Ser.No. 729,543 Int. Cl. Cm 1/48 U.S. Cl. 252-46.7 19 Claims ABSTRACT OF THEDISCLOSURE Two-cycle mineral lubricating oils having a viscosity of fromabout 58 to about 85 SUS at 210 F. contain a small but elfective amountof the amide condensation product of an alkenyl substituted alpha-betaunsaturated monocarboxylic acid of between about 800 and about 3500molecular weight and an alkylene polyamine together with a small buteffective amount of an antioxidant which is the sulfide of phosphorusreaction product of an oil-soluble compound selected from the groupconsisting of alpha monoolefin polymers and copolymers, terpenes, andsaturated and unsaturated primary and secondary C12-C20 alcohols, or theoils contain the sulfide of phosphorus reaction product of theaforementioned amide condensation product. Optionally, a lower viscositybase oil may have added thereto a sufficient amount of a viscosity indeximproving oil-soluble organic compound to achieve the above-definedviscosity of the oil composition. The oil compositions are used inadmixture with gasolines, in a volume ratio of oil to gasoline of l toat least 20, preferably 1 to at least 50.

The present invention concerns the manufacture of mineral lubricatingoil compositions which are primarily for use in two-cycle engines. Moreparticularly, the invention is concerned with mineral lubricating oilscontaining an ashless detergent type of material and also containing anantioxidant or the ashless detergent type material may be employed aloneif it has been so treated chemically as to give it also antioxidantproperties.

In recent times, the two-cycle, or what is sometimes called thetwo-stroke, engine has become extremely widely used for the powering ofchain saws, lawn mowers, small automobiles and has been used in outboardmotors for powering various types of boats. Because of the twocyclefeature of the engines, they do not have any provision for a crackcasenor for a pumped or forced oil flow circulating system, and so they mustdepend, for their lubrication, upon the presence of small amounts oflubricant admixed with the gasolines which fuels such engines. A largepercentage of the actual lubricant which enters the combustion chamberin the two-cycle engines by way of gasoline being fed into thecombustion chamber or chambers actually is burned along with the fuelbefore the oil has a chance to actually contact the piston rings orpiston walls. Also, one of the outstanding problems involved in the useof such oils in conjunction with such gasoline involves the frequent andprofound fouling of spark plugs, the clogging of exhaust ports, thedeposition of excess quantities of carbon in the combustion chamber, thetendency to preignition of the fuel and the like. Another disadvantageof this method of lubricating in this type of engine is thatconsiderable smoke and stench are created by reason of the exhaust gasesbeing emitted during the operation of the engine. If a sufficiently highconcentration of oil is placed in the gasoline to provide adequatelubrication, then the aforementioned disadvantages become morepronounced. If a lesser amount of oil is placed in the gasoline, thereis always danger of insufficient and defective lubrication of the enginewith the resultant danger to cylinder walls,

Patented Dec. 1, 1970 "ice piston rings, piston bearings and so forth.Furthermore, modern technology by the two-cycle engine manufacturers hasresulted in the production of high output, increased horsepower enginesrunning up to as high as and horsepower with the result that evencritical demands are placed upon the use of lubricants which will standup under the more rigorous conditions and more demanding performance ofsuch high power output engines. Also, the revolutions per minute of suchoutboard motors have been increased which means that in more cases theneed for improved lubrication of cooling and sliding surfaces to reducefriction between such moving surfaces is increased. Additionally, mostgasolines Widely sold commercially contain lead alkyl compounds asantiknock agents. The presence of lead in the gasoline in many instancesadversely affects the lubricating effectiveness of the two-cyclelubricating oils which have heretofore been employed. High temperaturesresulting from preignition and other causes such as improper cooling canalso lead to insufficient lubrication which, in turn, leads to excessivewear, high scufiing and scoring and even piston seizure.

There has been an increased need for a lubricating oil composition thatwill be more suitable than conventional motor oils for two-cycleengines, particularly for outboard motor service. Certain makes ofengines are more critical than others. 'In general, modern highhorsepower (i.e. above 18 horsepower, and particularly above 25horsepower) outboard motors produce more plug fouling problems than dolower horsepower models. Severe plug fouling conditions are presented byfull throttle operation with highly-leaded fuel (2 to 3 ml. per gallon).

A high-performance, two-cycle engine lubricant should be readilymiscible with gasolines and should (1) provide good lubrication (lowfriction, lower wear, and no deformation, scufiing, scoring or seizing)of the rubbing parts such as anti-friction bearings, rings, pistons andcylinders; (2) maintain a clean combustion chamber with attendant longspark plug life and freedom from preignition; and (3) minimizepower-robbing piston and port deposits. Also such a lubricant shouldprotect against rusting.

The novel two-cycle lubricating oil compositions hereinafter describedalso possess the virtue of being usable in higher gasoline to oildilutions than has heretofore been thought to be attainable. This isparticularly advantageous when used in conjunction with the higherhorsepower two-cycle engines because it has been discovered that thereis greater cleanliness, less chance of plug fouling and less smokyexhaust when using such higher dilution of gasoline to lubricating oil.Heretofore, higher concentrations of additives at a 50 to 1 volume ratioof gasoline to oil resulted in serious operating problems such aspreignition, exhaust port deposits and spark plug fouling. The ashlesstwo-cycle engine lubricating oils at this dilution more than adequatelycontrol the problems of preignition, spark plug fouling, exhaust portdeposits, smoky exhaust gases and the like. In fact, it is possible inthe lower horsepower two-cycle engines to employ gasoline to oildilution ratios of as much as 100 to 1 volume ratio with entirelysatisfactory lubrication being effected under such conditions.

The novel two-cycle mineral lubricating oil composition contains a majoramount of a base mineral oil which may be of any type, i.e. naphthenic,aromatic, paratfinic, or mixed, preferably paraflinic, having aviscosity at 210 F. of between about 58 and 85 SUS. Either the oilitself as blended may possess this viscosity or a solvent extractedneutral oil of a lower viscosity may be employed as a higher viscositylubricating oil fraction is added thereto to raise the viscosity of theresultant blend or a small amount, up to as high as 7.5 wt. percent of acon ventional V.I. improver may be added to accomplish the same purpose.Incorporated in this base stock or one adjusted to the indicatedviscosities is an amide which is the condensation product of a longchain alkenyl substituted alpha-beta unsaturated monocarboxylic acidhaving a number average molecular weight between 800 and about 3500 withan alkylene polyamine. These materials are old in the art having beenemployed as detergent and dispersant compositions in mineral lubricatingoils employed in lubricating engines opearting on the Otto cycle andwhere in a pumped circulating oil system including a filter iscustomarily employed. 'In addition to the amide condensation product,there is also added a small amount, up to about 7.5 wt. percent of asulfide of phosphorus reaction product of a compound selected from thegroup consisting of alpha monolefinic polymers and copolymers, terpenes,saturated and unsaturated primary and secondary C -C alcohols. Thismaterial serves as an antioxidant and while these materials have alsobeen employed in conventional mineral lubricating oils for Otto cycleengines as well, many other types of oil-soluble antioxidants do notperform a satisfactory function in two-cycle engine lubricating oils. Itis also possible to omit the use of this sulfide of phosphorus productas an antioxidant if the aforementioned amide before use is treated witha sulfide of phosphorus in which case the single compound then servesthe dual function of being a satisfactory dispersant and a satisfactoryantioxidant.

U.S. Patents 3,296,133; 3,290,130; and 3,310,492 all deal with theproblem of improving the lubrication of two-cycle engines while at thesame time seeking to avoid one or more of the aforementioneddifliculties in operating two-cycle engines where the lubricant issupplied to the engine by way of the gasoline fueling the engine.Individually, phosphosulfurized terpenes and phosphosulfun'zedpolyolefins such as polyisobutylene have been employed in two-cycleengine lubricants in conjunction with the alkaline earth metal organicsulfonates. Additionally, the polyisobutenyl succinic anhydride amidecondensation product with an alkylene polyamine has also been employedas an additive in two-cycle lubricating oil compositions but as the moredetailed description hereinafter shows the results have not been nearlyso advantageous in terms of eliminating the aforementioned problems ashave been achieved by the unique combination of additives in thehereindisclosed two-cycle engine lubricating oil compositions.

The base stock for two-cycle lubricating oil compositions should beclean burning and they should be of the aforementioned viscosities at210 F. Solvent refined neutral lube oil fraction distillates roughlycorresponding to SAE 30 and SAE 40 lubricating oils and preferably ofparafiinic nature constitute for the most part the desirable base stocksinto which one or more of the additives specified are incorporated. Thebase stock should have a viscosity index of from about 90 to about 100but higher viscosity index oils, up to 110 may also be used. The oilbase stocks should have particular low Conradson group residues, i.e. ofless than 0.1 wt. percent. Highly refined residual stocks such as brightstock burn less completely than the highly refined all distillate stocksbut these refined residual stocks are useful in limited amounts, i.e. tothe extent of from to volume percent of the total base stock fortwo-cycle engine applications.

The ashless detergent, i.e. the amide condensation product, is presentin an amount ranging between about 0.2 and about volume percent of thetotal lubricating oil compounded composition, preferably between about 3and about 15 volume percent. The amide material is conventional for thesake of completeness, however, it may be stated that it involves thecondensation of an alkylene polyamine with an alkenyl substitutedalpha-beta olefinically unsaturated monocarboxylic acid. This materialwill have a number average moleculer weight of between about 800 andabout 3500. and may be produced in a number of ways, for example, suchacids can be prepared by oxidizing high molecular weight olefins, i.e.polyisobutylene, of the required molecular weight with an oxidizingagent such as nitric acid or oxygen followed by the addition of analdehyde to the polymer. This addition product is then, in turn,oxidized or a halogen can be added such as chlorine or bromine to thehigh molecular weight polyolefin to form a dihalo compound which then istreated by hydrolyzing oxidation. These procedures are shown in BritishPatent No. 983,040. The same materials can be produced by oxidizing amonohydric alcohol with potassium permanganate or by reacting ahalogenated high molecular weight olefin polymer with a ketene. The samemonocarboxylic acids can also be prepared from olefin polymers such as apolymer, or copolymer of a C -C monoolefin, isolating from the productthe polymer of the desired molecular weight, halogenating the same andthen condensing it with an alpha-beta unsaturated moncarboxylic acid. Inother words, by intimately contacting chlorine or bromine withpolyisobutylene, polypropylene or ethylene/propylene copolymer, a halopolymer is formed. This is usually carried out in a suitable solventsuch as carbon tetrachloride at a temperature of 50- 300 F. and in about2 to 5 hours. The halogenated polymer is then condensed with themonocarboxylic acid which is usually from 3-8 carbon atoms, preferably34 carbon atoms. Because of commercially availability, acrylic acid andalpha methacrylic acid are the preferred acids although crotonic,isocrotonic, tiglic, angelic, sorbic, and cinnamic acids may be used aswell. Normally, one mole of acid is empolyed per mole of halogenatedpolyolefin, however, the acid is sometimes employed in molar excess tothe amount of halogenated polyolefin and may amount to as much as 1.5 toabout 2 moles per mole of halogenated polyolefin. The condensationtemperature ranges from between 300 and 500 F. and the time of reactionis from 3-24 hours, most preferably 6-18 hours. Any excess acid may beremoved from the reacted mixture by blowing with, nitrogen gas at 400500F.

The alkylene polyamine employed as one reaction in the amidecondensation reaction can be any of these which have been customarilyemployed in such reactions. They conform to the general formula:

wherein n is 2 to 4 and m is an integer from 0 to 10. Specific compoundscoming within the formula include diethylene triamine, triethylenetetramine, tetraethylene pentamine, dibutylene triamine, dipropylenetriamine, hexaethylene heptamine, octaethylene nonamine, andtetrapropylene pentamine. Other amines can also be used such as N (2aminoisopropyl)piperazine, N,N'di(2 aminoethyl) piperazine.

The proportion of the long chain alkenyl monocarboxylie acid, forexample, polyisobutenyl propionic acid to alkylene polyamine, forexample, tetraethylenepentamine, may range between about 1 to 5 moles ofacid per mole of polyamine, preferably between about 1 to 1 and about 3to 1. The reactions are carried out at a temperature of about 200-400 F.under conditions such as to drive off the water of condensation which isremoved by blowing with an inert gas such as nitrogen. Generally, thetemperatures are between about 250 and 350 F. and the time of reactionis between about 6 and about 20 hours. This amide material may be usedas such in conjunction with the hereinafter described antioxidants. Itmay also, however, be further treated with a sulfide of phosphorus suchas phosphorus pentasulfide, phosphorus sesquisulfide, phosphorusheptasulfide, and the like.

The same sulfides of phosphorus may also be used but preferablyphosphorus pentasulfide is employed for the treatment of terpenes suchas alpha pinene, for the treatment of alpha olefin polymers such aspolyisobutylene, or for the treatment of saturated or unsaturatedprimary or secondary alcohols whose alkyl or alkenyl radicals containfrom 12 to 20 carbon atoms. Unexpectedly, these materials serve assatisfactory antioxidants when used in conjunction with theaforementioned amide condensation product. Surprisingly, the amidecondensation product directly treated with phosphorus pentasulfideserves the dual function of an ashless dispersant and an antioxidant,however, it is within the scope of the present invention to employ notonly the amide condensation product in conjunction with one or more ofthe phosphosulfurized terpenes, polymeric olefins, or alcohols specifiedbut one may also employ both the amide condensation product and thephosphosulfurized amide condensation product. Further, one may employ amixture of amides employing different alkenyl carboxylic acids and adifferent alkylene polyamine or the same reactants but wherein the moleratio of the polyisobutenyl propionic acid, for example,tetraethylenepentamine, would be 1.8 to 1 instead of the preferred 2.8to 1. The amount of phosphosulfurized antioxidant employed will rangebetween about 0.5 and about 7.5 volume percent when it is employed. Thisis on the basis of a 50% concentration of active ingredient in a lightmineral oil. The amount of the amide condensation product employed,whether in phosphosulfurized form or not, will range between about 0.2and about 20 volume percent, preferably between about 3 and about volumepercent, again based upon a concentrate, having between about 65 andabout 75% active ingredient, with a light mineral base oil which is asolvent neutral paralfinic frac tion of about 150 SUS at 100 F.

Various types of viscosity index (V.I.) improvers which are conventionalin nature may also be incorporated into the two-cycle engine lubricatingoil compositions. These also serve in many instances as thickeners. Theyare chiefly used in those cases where the base oil has a viscosity below58 SUS at 210 F. for the purpose of adjusting the viscosity so that itfalls between 58 and 85 SUS at 210 F. These materials are well known andincludes the use of polyisobutylene, of a number average molecularweight ranging between about 100,000 and about 150,000, the use ofethylene/propylene, polyethylene, polypropylene, polymethylrnethacrylateesters, vinyl acetate, lauryl fumarate copolymers and various othertypes of polymeric materials which are equally well known in the art asadditives for lubricating oil compositions either for the purpose ofthickening oils or for improving their viscosity index, or for bothpurposes. Generally, these materials are, for convenience, handled asoil concentrates. In the following examples, the polyisobutyleneemployed has a number average molecular weight of about 100,000 and isgenerally marketed as a concentration in solvent neutral paraflinic oilhaving a viscosity of about 150 at 100 F. The amount of V1. improver orthickening agent will vary, depending upon the base oil used and in manyinstances where a blend of parafiinic lubricating oil is employed thefinal viscosity of between about 58 and 85 SUS at 210 F. will beachieved without the necessity for adding any thickening or V.I.improving agent. On the other hand, where lower viscosity base stocks orblends of base stocks are employed, a sufiicient amount of thethickening agent will be added so that the base oil will conform to theabovementioned viscosity specification since it has previously beendetermined that two-cycle engine oil lubrication compositions shouldhave the aforementioned viscosity specification.

Many of the commercially available gasolines which are customarilyemployed in operating internal combustion engines are suitable for usein admixture with the two-cycle lubricating oil compositions hereindescribed. These gasolines for the most part commonly contain betweenabout 0.5 and about 7.0 cc. per gallon, preferably 2.0 to 3.0 cc. pergallon, of alkyl lead anti-knock agents such as tetraethyl lead,tetrarnethyl lead, dimethyl diethyl lead or similar alkyl leadanti-knock agents. Other organo metallic additives can be employedcontaining lead, iron, nickel, lithium, manganese and the like. Otheradditives sometimes are employed such as antioxidants, corrosioninhibitors, anti-static agents, dyes, anti-icing agents, such asisopropanol, hexylene, glycol and the like, but these are conventionaland the successful use of the novel twocycle lubricating oil is notdependent upon the use of such conventional additives in gasoline. It isgenerally advantageous, however, to incorporate into the gasolineconcentrations of arylene or alkylene, bromides or chlorides inconcentrations of from 0.5 to 3.0 theories. For example, 0.8 to 1.5theories of ethylene dichloride, or 0.3 to 0.8 theories of ethylenedibromide are used as scavenger agents where the gasoline contains theorgano lead anti-knock agents. These are conventional practices and arenot particularly correlated with the novel combination of additivesemployed in the two-cycle lubricating oil compositions.

As before stated, the particular lubricating oil compositions hereindisclosed do, however, have a distinct advantage when admixed with theconventional gasolines used in operating two-cycle engines because ofthe fact that the gasoline to oil volume or weight ratios areconsiderably increased with entirely satisfactory results through theuse of these novel lubricating oil compositions. Whereas, in priorpractice, a 20 to l, 30 to l or even as high as a 40 to 1, gasoline tooil ratio was considered necessary in order to impart satisfactorylubrication in a two-cycle engine. The novel lubricating oil compositionherein described will achieve the same or even better lubricatingresults in a two-cycle engine where the gasoline to oil ratio is of theorder of 50 to 1, up to as high as to 1. In fact, this is one of theoutstanding advantages involved in the use of the herein described novellubricating oil compositions. As before stated, the lower theconcentration of lubricating oil in the gasoline fueling a two-cycleengine, the less the tendency for spark plug fouling, exhaust portclogging, or deposition and carbon and varnish formation on the cylinderwalls and pistons. All of these advantages even including the tendencytoward preignition are achieved without sacrificing the required minimumlubrication values for the operation of the two-cycle engine.

In the following examples, a series of comparative runs were undertaken,identified as Panel Coker Tests. These are primarily laboratory scale orbench tests designed to give a fairly good indication of what can beexpected in ultimate two-cycle engine tests. In this test, theparticular formulated two-cycle oil is splashed on the hot steel plate,maintained at a temperature of 550 F., and is then allowed to drain. Thecycle of operation consists of 15 seconds in which the oil formulationis splashed on the hot steel plate followed by a period of 45 secondsfor allowing the oil to drain from the plate. Thirty of these cycles insequence are preferred. In other words, the test in each case lasts for30 minutes total time. At the end of the test, the steel panel isweighed in order to determine the amount of deposition left on the steelpanel. This deposition is measured in milligrams. Additionally, thedegree of coke and varnish deposits left on the steel panel are visuallyrated with the scale being 0 where no deposits are found and the numeral10 being used where the entire surface is covered 100% with blackdeposits. This test in a preliminary manner determines the amount andextent of deposition formation and directionally indicates the depositforming tendency of the oil in two-cycle engine applications where thetemperatures in the piston ring zone often approach 550 F.

The following examples are given as illustrative of the character of theinvention but there is no intention that the invention be limitedthereto.

EXAMPLES In the following Table I the results are given for a number ofcomparative runs in Panel Coker Tests which are indicative of thepredicted performance of the various formulations when admixed withgasoline in at least a 50 to 1 volume ratio of gasoline to oil. Table Ishows comparative results using an ashless dispersant with or without anantioxidant some of which are conventional antioxidants.

TABLE I.-PANEL COKER TESTS NOTE.-polyisbutylene=20% concentrate ofpolyisobutylene (100,000 molecular weight) in solvent neutral base oilof 150 SUS at 100 F.; Additive A=65 70% concentrate of 2.8 mols 0tpolyisobutenyl propionic acid reacted w th 1 mol oftetraethylenepentamine (molecular weight about 900-1,000) 1n solventneutral base oil of 150 SUS at 100 F.; Additive B= Commerciallyavailable oil antioxidant-a mixture of 4,4 methylene bis (2,6 di-tert.butylphenol) and oil-soluble phenols; Additive C=Commerv It is readilyapparent that the phosphosulfurized antioxidants when used inconjunction with an ashless dispersant give unexpectedly excellentresults in so far as the amount of deposits are concerned and the extentof the deposits are concerned. In particular, Examples 5, 6 and 7 and inparticular Example 14 show outstanding results in this regard. It shouldalso be noted that conventional antioxidants, i.e. those commerciallyavailable and which have been universally accepted as outstandingantioxidants for lubricating oils as shown in Examples 8 through 13,employed conventional oil antioxidants which were inadequate whenemployed in conjunction with an ashless dispersant in so far as theiruse is applied to twocycle engine oils. It is also apparent from Example14 that no separate antioxidant is necessary if one uses aphosphosulfurized ashless dispersant as the additive to a two cycleengine lubricating oil.

A series of outboard engine tests were carried out, in

Weight of Ex. deposits, No. Base Oil Dispersant Antioxidant mgs. Rating1 76.3 vol ercent solvent neutral paratfinic of 18.7 vol. percentAdditive A- None 12. 9 7

200 S S at 100 F. plus vol. percent polyisobutylene. 2 dn dn 0.5 volpercent phosphosuliurized alpha 0 8 3 piglenfi as 50% concentration inlight miner 0 3 vol. percent Bright Stock 150 SUS at 210 15.0 volpercent Additive A" None.. 12. 3 5

F., 75 vol. percent parafinic neutral of 600 SUS at 100 F. 4 do do 0.1vol percent of Example 2- 11. 0 4 a do do 0.5 vol. percent of Example 26. 9 3 s rln rln 0.7 vol percent of Example 2 3. 8 2 7 do do 91.0 vol.percent of Example 2. 5 2 R dn do 0.2 wt. percent phenothiazine--- 7. 66 0 do do 0.5 wt. percent; N- benylalphanaphthalenm- 9. 3 8 10 do dn 0.5wt. percent A ditive B 11. 8 7 11 do dn 0 5 wt percent Additive 0-- 15.7 9 12 do do 0 5 wt percent Additwe D 15. 4 9 13 -do do 0.5 wt. percentAdditive E 1 4 ..do 5 vol. percent Additive F- Trace 0 cially availableoil antioxidant-4,4 bis (2,6 di-tert. butylphenol);Addil tiveD=Commercially available oil antioxidant-4,4 thio bis (6 tert. butylorthocresol) Additive E Commercially available oilantioxidantcondensation roduct of 2 mols of formaldehyde, 2 mols ofnonylphenol and 1 mol of ethylene triamine; Additive F=Additive Areacted with 10 wt. percent of P 8 general, in accordance with thebrochure entitled Tentative Test Procedures for Evaluating OutboardMotor Oils (two-cycle), Recommended Practices, published by the BoatingIndustry Association of Chicago, Ill. (1966).

Minor deviations from these procedures were made if through the use ofpolyisobutylene as described in connection with the oils used in thePanel Coker Tests (Table I). In all of the test runs, Examples 15-19, 15volume percent of the amide ashless detergent concentrate and 1 volumepercent of the phosphosulfurized pinene concentrate used in the PanelCoker Tests, were used, except that Run 16 used only one-half of theseamounts. All test runs passed the test limit specifications set by theBoating Industry Association.

TABLE IL-TWO-CYCLE OUTBOARD ENGINE TESTS [Fuel/Lube Oil Ratio: to1-Time: 981:0 100 hours] Example Number J ohnson-SO hp. J ohnson-33 hp.Johnson-100 hp. Mercury-50 hp. McCulloch (3- 4 9.5 (2-cycle)( 40.5 (89.5total (4-cycle) cycle) hp. (63 Engine total CID) total CID) CID) totalCID) total CID) Average engine test results:

Piston skirt, varnish (CRO) 8. 0 8. 6 6. 6 8. 5 7. 5 Top ringstickinii;l 7. 1 7. 5 6. 1 9. 5 6. 7 Bottom ring stic g 1 10. 0 10. 010. 0 10. 0 10. 0 Spark plug fouling, total No 2 2 1 5 7 None Exhaustpassage blocking, pereent-- 0 5 2 2 2 Exhaust port blocking, percent.4 1. 5 4. 5 0 0 Preignition None None None None None Sending/scoringNone None N one None None Total engine deposits, gms 54. 29. 8 34.

1 Ring sticking rating: 10 is completely free; 0 is fully stuck.

9 Surface gap plugs.

NOTES:

Examples 15, 16 and 19 employed premium grade gasoline. Examples 17 and18 used. regular grade gasoline. All gasolines contained from 2.6 to 2.9cc. per gallon of tetraethyl lead. Examples 15 and 16 only contained0.25 Theories of phosphorus added as cresyl diphenyl phosphate in thegasoline. Other examples used gasoline containing no phosphorus.

Examples 15, 17, 18 and 19 employed a base 0 cent of solvent neutral oilof 450 SUS at F ilblend of 10 volume percent of Bright Stock of Example3 and 74 volume per Example 16 employed the base oil blend of Example 3.

All examples employed 16 volume percent of phosphosulfurizedantioxidant, the same as t used in Example 16 Total CID refers to cubicinches, displacement for the total of all cylinders In another enginetest carried out substantially the same as in Example 15, but containingno P 8 treated alpha pinene, 8 total plugs failed and scufiing in No. 2and No. 4 cylinders was apparent. This test failed to meetspecifications.

Another test carried out as in Example 17, but the oil employed beingwithout P 8 treated alpha pinene, also failed by reason of a total of 12spark plugs fouled. There was scufiing of No. 3 piston skirt as well.

Still another comparative run was carried out after the manner ofExample 18 except no antioxidant was present in the oil. This showed atotal of 12 spark plugs fouled with heavy scufling and scoring ofcylinder walls and piston skirts.

A commercially available ashless dispersant additive for two-cycleoutboard engines was used in a test run as shown in Example except thatthe additive was in the amount of 5.7 volume percent in place of boththe 15.0 volume percent of the amide condensation product and the 1.0volume percent of the antioxidant used in Example 15. This test runfailed to meet specifications. It showed a total number of spark plugsfouling of 14 and some scuffing in No. 2 cylinder.

Having now thus fully described and illustrated the invention, what isdesired to be secured by Letters Patent 1. A two-cycle minerallubricating oil composition comprising a major amount of a base mineraloil of lubricating viscosity between about 58 and about 85 SUS at 210 F.containing between about 0.2 and about 15.0 volume percent of an amideof the group consisting of the condensation product of an alkenylsubstituted alpha, beta unsaturated monocarboxylic acid of between about800 and about 3500 number average molecular weight and an alkylenepolyamine and the sulfide of phosphorus reaction product thereof, as anantioxidant, between about 0.0 and about 7.5 volume percent of sulfideof phosphorus reaction product of a compound selected from the groupconsisting of alpha monoolefin polymers and copolymers, terpenes, andsaturated and unsaturated primary and secondary C -C alcohols, and fromabout 0.0 to about 7.5 volume percent of a viscosity index improver, thecomposition containing at least one sulfide of phosphorus treatedabove-stated organic compounds.

2. An oil composition as in claim 1 wherein the sulfide of phosphorus isphosphorus pentasulfide.

3. An oil composition as in claim 1 wherein the amide is thecondensation product of an alkenyl monocarboxylic acid of between about800 and about 3500 number average molecular weight and an alkylenepolyamine and wherein the composition contains a sulfide of phosphorusreaction product of a terpene and a poly alpha monoolefin as a viscosityindex improver.

4. An oil composition as in claim 3 wherein the sulfide of phosphorus isphosphorus pentasulfide.

5. An oil composition as in claim 3 wherein the composition containssufiicient oil-soluble viscosity index improver to achieve an oilcomposition viscosity of between about 58 and about 85 SUS at 210 F.,the base mineral oil being parafffinic and below the specified viscosityin unadulterated conditions.

6. An oil composition as in claim 3 wherein the amide is thecondensation product of polyisobutenyl propionic acid andtetraethylenepentamine and the antioxidant is phosphorus pentasulfidetreated alpha pinene.

7. An oil composition as in claim 6 wherein the composition alsocontains polyisobutylene of between about 100,000 and about 150,000number average molecular weight.

8. An oil composition as in claim 1 wherein the amide is thecondensation product of an alkenyl monocarboxylic acid of between about800 and about 3500 number average molecular weight and an alkylenepolyamine which is thereafter reacted with a sulfide of phosphorus.

9. An oil composition as in claim 8 wherein the sulfide of phosphorus isphosphorus pentasulfide.

10. A combined lubricant and fuel composition for the fueling andlubrication of two-cycle internal combustion engines comprising agasoline containing the oil composition of claim 1 in the amount of onevolume of oil to at least 20 volumes of gasoline.

11. A composition as in claim 10 wherein the oil composition alsocontains an alkyl lead anti-knock agent and a. halide scavengertherefor.

12. A composition as in claim 10 wherein the oil composition is that ofclaim 2.

13. A composition as in claim 10 wherein the oil composition is that ofclaim 3.

14. A composition as in claim 10 wherein the oil composition is that ofclaim 4.

'15. A composition as in claim 10 wherein the oil composition is that ofclaim 5.

16. A composition as in claim 10 wherein the oil composition is that ofclaim 6.

17. A composition as in claim 10 wherein the oil composition is that ofclaim 7.

18. A composition as in claim 10 wherein the oil composition is that ofclaim 8.

19. A composition as in claim 10 wherein the oil composition is that ofclaim 9.

References Cited UNITED STATES PATENTS 3,184,411 5/ 1965 Lowe 25246.72,721,862 10/ 1955 Brennan 25246.7 X 3,216,936 11/1965 Le Suer 4458 X3,310,492 3/1967 Benoit 4458 X 3,449,249 6/ 1969 Anderson 25259 FOREIGNPATENTS 983,040 2/1965 Great Britian. 1,417,499 10/1965 France.

OTHER REFERENCES Towle Lubrication Problems in Two-stroke Petrol EnginesScientific Lubrication, March 1959, pages 12-14 and 16-20.

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US.Cl. X.R. 44-5 8

